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[Display omitted] • Tix+ in-situ intercalation strategy via titanium foil/vanadium ion solution interface for long cycle LSB. • Inserted Tix+ can strengthen interlayer interaction so as to enhance lithium-ion mobility rate. • Mixed valence of V5+/V4+ reduces the stress and strain of lithium-ion intercalation. • Ti-VO 2.375 /S cathode delivers lower capacity decay with a stable coulombic efficiency. Lithium sulfur battery (LSB) has great potential as a promising next-generation energy storage system owing to ultra-high theoretical specific capacity and energy density. However, the polysulfide shuttle effect and slow redox kinetics are recognized the most stumbling blocks on the way of commercializing LSB. On this account, for the first time, we use Tix+ in-situ intercalation strategy via titanium foil/vanadium ion (V5+) solution interface to modify the layer of vanadium oxide for long cycle LSB. The inserted Tix+ strengthens interlayer interaction and enhances lithium-ion mobility rate. Meanwhile, based on density functional theory (DFT) calculation, the mixed valence of V5+/V4+ in the vanadium oxide structure reduces the stress and strain of lithium-ion intercalation through the interlayer support of titanium ions (Tix+). Also, Tix+ refines the structural stability of the sulfur wrapped composite matrix so as to facilitate the LiPSs transformation, and improve the electrochemical performances. Consequently, the Ti-VO 2.375 /S cathode delivers a lower capacity decay of 0.037 % per cycle over 1500 cycles with a stable coulombic efficiency around 100 %. [ABSTRACT FROM AUTHOR]

• The obstacles of lithium sulfur batteries (LSBs) and the important role of catalysts were introduced. • The research progress of phosphides doped with different cations in LSBs was elaborated. • The current synthesis methods of metal phosphides were summarized. • The applications of different metal phosphides were comprehensively introduced in the design of cathode sulfur carrier materials, modification of separator, and Li anode protection. • The challenges of using metal phosphide catalysts in commercial LSBs and design strategies to promote their commercialization were proposed. Lithium-sulfur batteries (LSBs) are widely acknowledged as the most promising energy storage systems for the future, primarily due to their remarkably high theoretical energy density. Nonetheless, the advancement of LSBs encounters various hurdles, including the substantial expansion of the cathode material, inadequate conductivity of the active material S and discharge product Li 2 S, the evident shuttle effect of lithium polysulfide (LiPS), and the sluggish sulfur conversion kinetics. These challenges become particularly evident when handling high sulfur loading. The issue of uneven Li dendrite growth at the anode significantly affects the long-term functionality and safety of batteries. Consequently, there is a pressing requirement for battery designs that effectively tackle these challenges. Metal phosphide, owing to its remarkable catalytic activity and distinctive physicochemical properties, has been extensively investigated and is anticipated to serve as a bifunctional material in LSBs systems. By manipulating the composition of cations, it is possible to obtain monometallic phosphide, bimetallic phosphide, and trimetallic phosphide through tailored design approaches. It has been found that metal phosphide catalysts can effectively adsorb soluble LiPS and catalyze its rapid conversion. Moreover, the synthesis of composite materials by incorporating metal phosphides with other compounds results in a synergistic effect that significantly improves catalytic performance. This study offers a thorough overview of the diverse applications of metal phosphides in enhancing cathode sulfur support materials, modifying separators, and protecting lithium anodes. The significance of metal phosphides in facilitating the anchoring of lithium polysulfides, improving electrochemical reaction rates, facilitating the nucleation and dissolution of lithium sulfide, enhancing electron and ion transport, and promoting uniform lithium deposition was underscored. Additionally, the obstacles and potential opportunities for metal phosphides in future lithium-sulfur batteries are examined, along with their practical utility. [ABSTRACT FROM AUTHOR]